Manufacture of catalysts



im M '1 4 2,289,918 I far-Basis YM ANUFAOTUBEOF CATALYSTS Edward C. Lee and JacobElaton Ahlberr, Chig cago, 111., asalgnon Universal Oil lfroducts Company, Chicago, llhacorporation c! Delai i No Drawing. Application October 31, 1938, i v v -SerialNo.'238,I7L

c p (c rca- 254): I v v v This invention relates particularly to the antilrnoclr value and gases containing-relatively q 1 a i manufactured catalysts suitable for accelerat high 'percentages c: readily polymerizable oleflns ing reactionsiamonghydrocarbons. V i i by preparing inthe primary-stepa m'iirtm'e otfl Mcrespeciiically itihas reference to a method 1 hydrated 'zirconia and hydrated silica to form for manufacturing refractory catalytic mute-r hydrated zirconia-sili'ca" masses of varying ziry rials which are particularly eii'ective inselecconic-silica ratios, and} subsequently treating tively promoting the formation of gasoline; boiland washing the compositemassesto eil'ect subing range liquids i'rom relativeLv heavy petroleum stantiallyfcomplete removal of alkali metal ions fractions. r i i v- "therefrom, then drying to removeamalorpor The art 1 "of pyrolyt'ically cracking relatively 510 tionlot the water contentMorming into particles heavy hydrocarbons tocproduce primarily r8380, yot'defl'nite sizesand lcalciningrthe purified catsline or gas is very extensive and-it is'recognized l'ytic material 1 n that most of the basic principles of hydrocarbon We have found that zirconia silica catalysts Kdecomposition are known and; that particular whichunay beprepared byseveral alternate i commercial processeshavebeen-developed which methods in the primary' tep of our process r embody these principles. The application oi-r de c' d' n 1 1 flthe succeedina NI I catalysts, however, .incracking reactions is pracgraphs, are rendered much m ore stable overl'ong tically upon the suuic basis as itisin other periods, or usaand l o? m f 1 1 ilelds that gis, it is largely empiricaly A consid: j l r nssaso ine o i a reactions erable number of catalysts tried out in. cracking in crackingwhen' the originally precipitated by; haves tendency toaccelerate reactionsflleading dratedizirconiaand h d a ed l v ls t0 i to the {urination cigas rather than .gagoline iormthe primarycompositesinvarious proporv this i being particularly evidencedby reduced tionsmre n i ly-fr from alk li m t l i metal catalysts, such as nickelor iron, and many u ions which in the mcrese 1pm? of such catalysts are sensitive tosuliur poisoning i i e so um i inasmuch a he, y and are. quickly coated-with carbonaceous mut I various sodium silicates comprise one of the more rials which render them practically inert; This fly available raw mate i s th 'l fl deposition of carbonaceous materialsistrequently I actu Of this 'llpe 0! catalyst; 'llhelfl i i frelated to the type of decomposition reactions t p in theceneraL m thod 0! .prepa a $1181 selectively fostered by thecatalyst.

" I v -catalysts which characterize the present inven- 1 The present invention is concerned with the tlvnvma'vibe va somewhatand the '1 I manufactureof catalytic materials. which are nc is a s mmarym e of'vtheclalternative specially adapted to accelerate the cracking, of 7 m des of operation which may bermpl y di heavy fractions or petroleum and other',hydro- 1 f 301111510115 0! jQ P m m re usucarbonaceous materials to increase the rate 01*35 y alkali lS lic nd l ble Zirconium production of high antiknoclr gasoline "boiling fl Q Y bezmixed under 're a te d ii o s range fractionsjandgaseous by-products fwhich of acidity orubasiclty to jointlyprecipitatehycontain unusually high percentages oi readily-1 (hated-Czirconiaandhydrated,;silica in" varyin i polymerizablejoleflns which areapotential source l P portions. i or further-gasoline yields. The preferred cata-"-,, 40 (2) Hydrated si i a hydrated i ia' -1 lysts are characterized by selectivity in accelmaybe separatelyprecipitated and the precipij crating gasoline-forming reactions rather than tates mixed in the wetcondition; :In thevcase light gas-forming reactions; by their selectivity i a convenient odis to iacidify a l l in producing high antiknock gasoline, by their solution oian alkali metal silicate to precipitate refractory character which enables theinto re- & sei. In thefcase 0t z co a', the desired A tain their catalytic properties undersevere con- Y hydroxide may be p ec p i fl fid by e addition ditions of temperature and pressure, b 11 1; of alkaline materials generally or volatile basic ease and simplicity of manufacture and their ex- "prec nita ts; suc as a onium h d xide, or act reproducibility." 1 ammonium carbonate; ammonium hydrosulflde,

i In one specifici mbpdiment t prcgent i r "ammonium sulfide, or othenvolatile basicpre-' tion comprises the manufacture of catalysts suitpi n generally y be p y able for use in hydrocarbonconversion reactions, (3) A sep ely pr cipitated hydrated silica more particularly theconversidn 0t hydrocargmaybe added to anaqueous solution or a{ zirboniractions containing substantially no gasoconium salt andthehydrated zirconia precipiline into substantial yields of gasoline of high tated in the presence of the suspended silica by two relatively dilute solutions.

the addition of alkaline materials generally orvolatile basic precipitants.

(4) A separately precipitated hydrated zirconia may be suspended in a solution of an alkali metal silicate and the silica precipitated in the presence of the suspended zirconia by the addition of just the required amount of acid which is insumcient to redissolve the zirconia.

It can be seen from the above that any method of obtaining a primary mix of hydrated silica and hydrated zirconia may be employed within the scope of the present invention, although obviously the character and eiiiciency of the ulti-' mately prepared zirconia-silicacatalysts will vary more or less with the exact conditions of precipi' tation and/or mixing, purification treatment, and

the ratio of zirconia to silica. For example, one

preparation may furnish catalysts best suitedv for use in the cracking of heavy hydrocarbon fractions, another may be better adapted .for use in p reforming hydrocarbonssubstantially within the gasoline boiling point range, while'cstill another preparation may be better adapted for still other hydrocarbon reactions., 1 In the catalysts thus prepared the ratio of silica to zirconia by weightmay range from 1 to' l, to 10 tojl or greater ratios may be used, active cat alysts having'been prepared in which theratio is as high as 50 tolzso that in effect thezirconia may be considered-to actas a promoter ofthe catalytic activity of the'silica. It is to be recognized that very little is known positively concerning the mechanism of promoter action in catalysts and no attempt will be made herein to offer any definite reason'for the observed effect of the addition of varying amounts of zirconia to silica. There may be a Joint promoter effect or it may be that the zirconia is the more active catalystiand is extensively dispersed in and on the silica in order to present a large surface.

In the case of co-precipitation carried outaccording to the general methods given in section 1 above, the final acidity or basicity of the aqueous menstruumin which the precipitation is carried out should correspond to a pH value of approximately 310 in order to obtain best results. This can be accomplished by calculating the requisite amount of acid or alkali which may be added to a certain volume 0! water in which the precipitation" is brought about, by the simultaneous and gradual addition of more concentrated solutions of zirconiumand silico'n'compounds, or it may be previously added to either solution in case precipitation is brought about by the i An important feature of the present invention resides in the fact that catalysts of greatly increased stability and efficiencyin cracking reactions are produced when there is substantially complete exclusion of alkali metal ions, from the hydrated zirconia-silica masses prior to their drying and calcining to'prepare them for service.

It is not known positively whether the alkali metal compounds, such as those of sodium, are present in theprimary hydrated composites in chemical combination or in anadsorbed state, but it has been definitely determined that their exclusion or removal is necessary if catalysts of superior activity andstability are to be obtained.

It may be considered that the presence of 'these alkali metal ions may cause a sintering or fusion of the surfaces of theprimary composites of the catalytic material at elevated temperatures so ,that the porosity of the catalyst particlesis reduced or altered with a corresponding mduction mixing Of in effective surface, considering the catalytic effects to be due at least in part to surface action. However, such concepts are principally speculative in view of the difiiculty of obtaining direct confirmatory evidence.

Several alternative methods are applicable to differentprimary hydrated silica-hydrated zirconia composites to insure the substantially complete absence of sodium or other alkali metal ions. One method consists in treating and washing the primary hydrated silica-hydrated zirconia precipitates or composites with regulated quantities of acidic solutions to extract alkali metal compounds incorporated into the composite catalytic materials during preparation by the formation of correspondingalkali metal salts and possibly introducing hydrogen ions into the catalyst composites. Thus a precipitated hydrated silica-hydrated zirconia mass may be first washed with water to remove the major portion of the soluble impurities and subsequentlytreated with relatively dilute hydrochloric acid, for example, and water to remove the alkali metal ions. As an alternative-purification method, the primary composites may be treated with ammonium compounds or'salts, such as ammonium chloride in solution or other ammonium halides, the sulfate, the nitrate, or the acetate so that alkali metal ions will not be substantially present in the composite when the composite preparation has been suitably washed. Whether the alkali,

metal ions are present in the hydrated zirconiahydrated silica mixture in a chemically combined or adsorbed condition, the alkali metal ion may be replaced by the ammonium ions which will be later expelledfrom combination or adsorption in subsequent treatmentat elevated temperatures. As a variation of this method the coprecipitation of the primary hydrated siiica'and hydrated zirconia may be brought about in the presence of ammonium hydroxide, or any of the other-salts of ammonium already mentioned, in

*sufllc'ient excess to insure an adequate removal of the alkali metal ions. In the case of co-precipitation, when using alkali 'metal silicates it [has been found when admixing larger amounts of zirconia that the necessary excess of ammonia is present at the point corresponding to the presence of a gel structure of the primary precipitate which permits ready filtering and washing. In other words, if suflicient ammonia has been used to insure easy washing and filtering, the al- 'kali metal ions have been generally removed to a degree at which they no longer have any appreciable adverse influence on the catalyst properties. In these methods of preparing the primary composite and in subsequent methods given .below, it will be apparent that the purifying treatment may be introduced in the presence of the original reacting materials, orsubsequent to the removal of soluble salts by preliminary treatment as, for example, by filtering and water washing.

. The weight of evidence at hand on the mechanism leading to the replacement of alkali metals in the primary hydrated silica-hydrated zirconia masses indicates that the alkali metals are held by adsorption rather than by chemical bonds. This is indicated by thefact that the alkali metal ions are replaceable by ammonium or multivalent positive ions which are known in general to be more strongly adsorbed than alkali metal ions.

This diflerentiates this replacement from the base exchange that occurs in the case of zeolites.

metal ions fromprecipitated hydrated silica-hy-v drated zirconia composites; consists in ftreatingsuch composites with salts ofi metals whichejmay replace thefsodiurii or other alkali metals in manner similar tothat describedinfltheoase i: ammonium compounds. 1 li ior exanip le,apprirna composite havingjlarge amountsjot-"alkalimetal whe nf employed as tffllling mai compounds; presentj alsoi a primary composite terialfinj tubes 1 or chamberszin' theiorm oi" pellets v containinundesirably lareefani ntsotadsdrbe r ranules; t ee nl 's e b mwherematerial and" isnot removed at elevated temper 1 aturesfias 1 is 'the ammonium; above ;described;

whatsoever the purification 'methodjusedif' ca alysts suitable for hydrocarbo i *may be obtained by the 'I'he purification? methods hi been given above have'ibeen; illustrated v r in connection withhreparations p hydratedzirconia hydrafed sections 1 and 2 noted:

cording to variationsoffse hydrolysis of the zirco "zirconia precipitated,

conium salt solution m i of the primary compo Another alternate method .ofreinoving as ye: the spent parn deposits rcarbonaceous mateas1400 to 1600 F.

v 4 catalytic activity, r em B8* Qzm-P'9 o e catalysts pared 'thekeneralprocedure describedin'the precedingparagraphsfiare;utilizedto advantage in "hydroearbonitractions vaporizable at v I ratemm rw' ihime ten q I DOS NQP employed the -average 7 Par icle size 1 x alkali metal ions introduced mtbtnicmlfyae above described.

arately precipitatedhyd to a zirconium salt sol conia deposited with-L silicate solution" andhth in the presence of th conia. Whatsoever'th'e method above described i a V ,iri'gand removing impurities.

found that aiter tlie usualf ity of the catalyst isfobtainedifand alurther a long period of service, they are diiiicultto refr m the primed m terial. These particles were reactivation as evidenced by the iactthat the After the finaiwas hydrated silica m-ixtu v p I filter cake and; dried temperatu shapes by compression me (is material usually has altotalwater I H proximately per-cent ,wm napp ers co spond to the bestflworkabilityfot; thelmaterial. By calcining the particles attempe'ratures o! the order of 850-1000? (E. or higher maxiniumacti is he precipitatedxnass' te all sdspendcdin as te anditheir again peration'being rel nes ubsequently theprecipim @M-biii sp zia museums: am-- v p 33cc. oiconcentrated ammoniumhydrofldefmr the removal of alkali metai saitsq The-"catalvtic material was then itered'andfthe ammonium chloride treatment f repeated; subsequentiythematerialwaswashed with three 5 liternportions of water and then vapors are able to v "iiltered the filter cake being subsequently dried distance and yet not s smalltha henthe pores a pp o y e dried material was become clogged with carbonaceous depositslatter 'j then p essed' nd particles 01' 0 es p odu ed dehydration occurs so that, for example,- attera period of heating at 9009-11, the'waterjcontent as determined by analysis is oi the lorderof .2 tog3 percent which doesjnot vary'appreciably either as the result of long serViceflbr a largenumber of reactivations at considrably' higher tern Catalysts preparl cedure evidentlypo'sse activate by oxidation. This structure is alsorethen calcined at approximately 932 E. and distained after many alternate periods of use and posed in a catalyst chamber for a test. A Pennsylvania gas -oil was vaporized and the vapors catalyts may be repeatedly reactivated by passing preheated to a temperature of 932? F. and passed through the catalyst bed at a liquid space velocity per hour of approximately 4. In a once-through operation 27.5% of 400 F. end-point gasoline wasproduced having an octane number 78.3.

Readily polymerizable olefin hydrocarbons of 3 and 4 carbon atoms were also produced corresponding to 4.5% by. volume oi the original charge. Ina second pass alter regeneration of the catalyst with air 28.9% gasoline wasproduced having an octane number of 'I8.2.

Example 11 v The procedure in the present example consists in adding a solution or zirconyl chloride to an aqueoussolution of sodium silicate and subsequently adding ammonium hydroxide.

.'One and one-half liters of a solution oi! ZrOCiz,

corresponding to 0.48 mole ZrOa is slowly added whileagitating to one and one-halt liters oi. sodiumgsilicate solution (Na:SiOa.9H:O), correspending to 3.0 moles or 810:. An ammonium hydroxide solution is then gradually added while stirring until the liquid'is alkaline to litmus.

, After standing for a short period the precipitated material is filtered and theiiiiter' cake slurriediin liters of a solution containing 14 grams of ammonium chloride and 3 cc. of concentrated ammonium hydroxide per liter. After 1 agitation for about 15 minutes the material is porting 16 moles of ZrOz.

When processing a paramnic gas-oil over this catalyst at approximately 932 ,F. in a oncethroughoperation, a yield of by volume of 400 F. end-point gasoline maybe produced having an octane number of 78 with a yield of readily polymerizable oleflns of 3-4 carbon atoms corresponding to approximately 4% by volume of the original charge.

We claim as our invention: 1. A process for the manufacture of catalysts for use in hydrocarbon conversion reactions, which comprises concurrently precipitating hydrated zirconium oxide and hydrated silicon dioxide bythe interaction of solutions of alkali metal silicate and zirconium compounds in an aqueous menstruum containing suiilcient acidic or alkaline reagent to produce a final pH of 3- 10; ireeing the precipitated materialsubstantially completely of alkali metal'ions, then heating sufliciently to remove a major portion of the water content, forming particles 01' definite size. and calcining above a temperature of about 800 F. I

2. A process for the manuiacture oi catalysts tor-use in hydrocarbon conversion reactions.

drated zirconium oxide and hydrated silicon dioxide by'the interaction of solutions of alkali metal silicate and zirconium compounds'in an 1 drated zirconium oxide and hydrated silicon dioxide by the interaction of solutions of alkali metal silicate and zirconium compounds in an .aqueous menstruumcontaining suflicient acidic or alkaline reagent to produce a final pH of 3-10, treating the precipitated material with a suilicient quantity of an ammonium compound and water to-substantially completely remove alkali metal ions, heating the treated precipitates to remove a major portion of the water content, i'orming particles 01 definite size, and calcining above a temperature of about 800 F.

4. A process for the manufacture of catalysts for use in hydrocarbon conversion reactions, which comprises concurrently precipitating hydrated zirconium oxide and hydrated silicon dioxide by the interaction of solutions of alkali metal silicate and zirconium compounds in an aqueous menstruum containing suflicient acidic or alkaline reagent to produce a final pH of 3-10, treating the precipitated material with a suiiicient quantity 01' a salt-oi a multivalent metal and water to substantially completely remove alkali metal ions, heating the treated precipitates to remove a major portion of the water content, forming particles of definite size, and calcining above a temperature of about 800 F.

EDWARD C. LEE. 7 JACOB EISTON AHLBERG. 

